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(11) | EP 2 005 453 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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ELECTRET MATERIALS ELECTRETMATERIALIEN MATÉRIAUX À ÉLECTRETS |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
[0001] The present invention is aimed at electret compositions having excellent thermal stability and charge stability. The electret compositions are, for example, polyolefin fibers or films and are suitably employed as filter materials, wipes, absorbent materials, filter masks, acoustic materials, printing substrates, measuring devices or contactless switches.
[0002] Electret (formed of elektr- from "electricity" and -et from "magnet") is a dielectric material that has a quasi-permanent electric charge or dipole polarisation. An electret generates internal and external electric fields, and is the electrostatic equivalent of a permanent magnet (Wikipedia Definition, Entry Electret: Last modified 22th Feb. 2007).
[0003] U.S. Pat. Spec. No. 5,057,710 discloses electret materials comprising hindered amines, nitrogen containing hindered phenols or metal-containing hindered phenols. WO 01/26 778 discloses a method for preparing an electret composition wherein a thermoplastic polymer is melt blended with a hindered amine compound, and the blend is subjected to an electret treatment.
[0005] U.S. Pat. Spec. No. 6,123, 752 discloses high efficiency filter medium containing a performance enhancing additive.
[0006] U.S. Pat. Spec. No. 6,743,464 discloses a method of making electrets through vapour condensation.
[0009] Subject matter of the invention is an electret composition as defined by claim 9, with enhanced thermal and charge stability, which composition has been subjected to an electret treatment, comprising a thermoplastic polymer and incorporated therein, an effective stabilizing amount of at least one hindered hydroxylamine ester compound, which compound contains at least one moiety of the formula I
Where
Ra' is a monoacyl or diacyl radical;
R1 - R4 are each C1-C6alkyl; and
R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl; or
R5 and R6 are together oxygen.
[0011] Also disclosed is a method for preparing an electret composition as defined by claim 1, with enhanced thermal and charge stability, which method comprises melt blending a thermoplastic polymer with an effective stabilizing amount of at least one hindered hydroxylamine ester compound, which compound contains at least one moiety of the formula I, as defined above, and subjecting the blend to an electret treatment.
[0012] The thermoplastic polymer is a non-conductive polymer that has the capability of possessing a non-transitory or long-lived trapped charge. The polymer is, for example, a polyolefin, a halogenated vinyl polymer (e.g. polyvinyl chloride), polystyrene, polycarbonate, a polyester (e.g. polyethylene terephthalate), a polyamide or a fluoro-polymer (e.g. polytetrafluoroethylene).
[0013] The thermoplastic polymers are, for example, propylene homopolymers, propylene copolymers and polypropylene blends. Propylene copolymers may contain various proportions up to 90.0%, preferably up to 50.0%, of comonomers. Examples of comonomers are: olefins such as 1-olefins, e.g. ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene, isobutylene, cycloolefins, e.g. cyclopentene, cyclohexene, norbornene or ethylidenenorborne, dienes such as butadiene, isoprene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene or norbomadiene; also acrylic acid derivatives and unsaturated carboxylic anhydrides such as maleic anhydride.
[0014] Polypropylene blends which can be used are mixtures of polypropylene with polyolefins. Examples are blends of polypropylene with polyethylene selected from the group consisting of high density polyethylene (HDPE), high molecular weight high density polyethylene (HMW HDPE), ultra high molecular weight high density polyethylene (UHMW HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) and ethylene-propylene-diene terpolymers (EPDM) containing small proportions of diene.
[0015] The polymer is especially a polyolefin, for example, polypropylene, poly(4-methyl-1-pentene) or linear low density polyethylene, or blends or copolymers thereof. The polymer may be a blend of a polyolefin and a polymer that contains polar groups, for example a polyester or a polyamide.
[0016] The electret composition comprising the thermoplastic composition is in the form of a non-woven web, a film, or a woven fabric. The electret composition is in particular a non-woven fibrous web.
[0017] The electret treatment may be any known treatment. Electret treatments are taught, for example, in U.S. Pat. Spec. Nos. 5,057,710, 5,556,618, 6,123,752, 6,743,464, 6,969,484, 6,284,339, 5,256,176 and 6,926,961. The electret treatment is any exposure to electricity, for example hydro-charging, tribo-electric charging or corona treatment. The electret treatment is especially a corona treatment.
[0018] An electret composition according to this invention is a thermoplastic composition that has been subjected to an electret treatment.
[0019] The hindered hydroxylamine ester compounds are disclosed, for example, in U.S. Published App. No. 2003/0216494.
[0020] The present hydroxylamine ester compounds contain at least one moiety of the formula I
Where
Ra' is a monoacyl or diacyl radical;
R1 - R4 are each C1-C6alkyl; and
R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl; or
R5 and R6 are together oxygen.
[0021] Preference is given to compounds containing the moiety I, in which Ra' is C2-C18alkanoyl or C3-C6alkenoyl.
[0023] A monoacyl radical Ra' may be, for example, the acyl radical derived from a monobasic organic acid comprising C radicals and an acid function, e.g. one of the above-defined acyl radicals of the partial formulae -C(=O)-H, -C(=O)-C1-C19alkyl, -C(=O)-C2-C19alkenyl, -C(=O)-C2-C4alkenyl-C6-C10aryl, -C(=O)-C6-C10aryl, -C(=O)-O-C1-C6alkyl,
-C(=O)-O-C6-C10aryl, -C(=O)-NH-C1-C6alkyl, -C(=O)-NH-C6-C10aryl and
-C(=O)-N(C1-C6alkyl)2.
[0024] When Ra' is a monoacyl radical, hydroxylamine esters containing group (I) are monomeric or dimeric structures. Thus, dimeric structures have suitable bivalent substituents in the 4-position and these are in turn substituted in the terminal position by compounds (I) via their 4-position (α,ω-substitution).
[0025] The term hydroxylamine ester encompasses both monomeric and oligomeric compounds and also polymers formed by compounds of the formula I.
[0026] A diacyl radical Ra' may be, for example, the diacyl radical derived from a monobasic organic acid having C radicals and two acid functions, e.g. a diacyl radical derived from an aliphatic, aromatic or cycloaliphatic dicarboxylic acid.
[0027] Suitable aliphatic dicarboxylic acids have from 2 to 40 C-atoms, e.g. oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid and dimeric acid (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acids, e.g. octadecylsuccinic acid.
[0028] Suitable cycloaliphatic dicarboxylic acids are, for example, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-(dicarboxymethyl)cyclohexane or 4,4'-dicyctohexyldicarboxylic acid.
[0029] Suitable aromatic dicarboxylic acids are, for example, terephthalic acid, isophthalic acid, o-phthalic acid, and also 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, bis(4-carboxyphenyl) sulphone, 4,4'-benzophenonedicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxylphenyl)indane, bis(4-carboxyphenyl) ether, bis(p-carboxyphenyl) methane or bis(p-carboxyphenyl)ethane.
[0030] Preference is given to aromatic dicarboxylic acids, in particular terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
[0031] Further suitable dicarboxylic acids are ones containing -CO-NH- groups. These are described in U.S. Pat. Spec. No. 4,002,600. Also suitable are dicarboxylic acids containing N-heterocyclic rings, e.g. those derived from carboxyalkylated, carboxyphenylated or carboxybenzylated monoamine-s-triazinedicarboxylic acids, cf. U.S. Pat. Spec. No. 3,697,520 and U.S. Pat. Spec. No. 4,034,019, mono-hydantoins or bis-hydantoins, halogenated or unhalogenated benzimidazoles or parabenic acid. The carboxyalkyl groups may contain from 3 to 20 C-atoms.
[0032] When Ra' is a diacyl radical and a suitable functional group, e.g. hydroxy or amino, is present in the 4-position, compounds containing groups of the formula I are polymeric structures, e.g. polyesters, polyesteramides, polyurethanes, polycarbonates or polyimide esters.
[0033] For example, the hindered hydroxylamine esters are of the formula IA
Where
n is an integer from 1 to 4,
Ra is acyl and R1', R2 and R3' are each, independently of one another, hydrogen or methyl; and G has the following meanings:
When n = 1,
G is hydrogen, C1-C18alkyl which may be interrupted by at least one oxygen atoms, 2-cyanoethyl, benzyl,
glycidyl, the monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated
or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent
silyl radical, preferably the acyl radical of an aliphatic carboxylic acid having
from 2 to 18 C-atoms, of a cycloaliphatic carboxylic acid having from 7 to 15 C-atoms,
of an α,β-unsaturated carboxylic acid having from 3 to 5 C-atoms or of an aromatic
carboxylic acid having from 7 to 15 C-atoms, where the carboxylic acid may be substituted
in the aliphatic, cycloaliphatic or aromatic part by from 1 to 3 -COOZ1 groups, where Z1 is hydrogen, C1-C2oalkyl, C3-C12alkenyl, C5-C7cycloalkyl, phenyl or benzyl; or
When n = 2,
G is C2-C12alkylene, C4-C12alkenylene, xylylene, the divalent acid radical of an aliphatic, cycloaliphatic, araliphatic
or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid, or a
divalent silyl radical, preferably the acyl radical of an aliphatic dicarboxylic acid
having from 2 to 36 C-atoms, of a cycloaliphatic or aromatic dicarboxylic acid having
from 8 to 14 C-atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid
having from 8 to 14 C-atoms, where the dicarboxylic acid may be substituted in the
aliphatic, cycloaliphatic or aromatic part by 1 or 2 -COOZ1 groups, where Z1 is as defined above; or
When n = 3,
G is the trivalent acid radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic
acid, where the radical may be substituted in the aliphatic, cycloaliphatic or aromatic
part by -COOZ1, where Z1 is as defined above, or the trivalent acid radical of an aromatic tricarbamic acid
or a phosphorus-containing acid, or a trivalent silyl radical; and
When n = 4,
G is the tetravalent acid radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic
acid.
[0035] Where n is 1 or 2, R1', R2' and R3' are each hydrogen and Ra is C2-C18alkanoyl or C3-C6alkenoyl and G is the acyl radical of an aliphatic monocarboxylic acid having from 12 to 18 C-atoms or the diacyl radical of an aliphatic dicarboxylic acid having from 4 to 12 C-atoms.
[0036] G defined as C1-C18alkyl may be as defined below or may, for example, be n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[0037] A monovalent acyl radical of a carboxylic acid as G may be, for example, the acyl radical of acetic acid, hexanoic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid; preferably the acyl radical of stearic acid, acrylic acid or methacrylic acid.
[0038] A monovalent silyl radical G may be, for example, a radical -(CnH2n)-Si(Z')2Z", where n is an integer from 2 to 5 and Z' and Z" are each, independently of one another C1-C4alkyl or C1-C4alkoxy.
[0039] A divalent acid radical of a dicarboxylic acid as G may be, for example, the acid radical of malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid or bicycloheptenedicarboxylic acid.
[0040] A trivalent radical of a tricarboxylic acid as G may be, for example, the acid radical of trimellitic acid, citric acid or nitrilotriacetic acid.
[0041] A tetravalent radical of a tetracarboxylic acid as G may be, for example, the tetravalent acid radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
[0042] A divalent radical of a dicarbamic acid as G may be, for example, the hexamethylenedicarbamic acid radical or the 2,4-toluylenedicarbamic acid radical.
[0043] Preferred compounds are compounds (IA), in which n is 1 or 2, R1', R2' and R3' are each hydrogen and Ra is C2-C18alkanoyl or C3-C6alkenoyl and G is the acyl radical of an aliphatic monocarboxylic acid having from 12 to 18 C-atoms or the diacyl radical of an aliphatic dicarboxylic acid having from 4 to 12 C-atoms.
[0044] The hydroxylamine esters may be of the formula IB
Where
n is 1 or 2 and Ra, R1', R2' and R3' are as defined under the formula IA;
G1 is hydrogen, C1-C12alkyl, C2-C5hydroxyalkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-C18alkanoyl, C3-C5alkenoyl or benzoyl or a group:
G2 has the following meanings:
When n=1,
G2 is hydrogen, C1-C18alkyl, C3-C8alkenyl, C5-C7cycloalkyl, C1-C4alkyl which bears a hydroxy, cyano, alkoxycarbonyl or carbamido group as substituent,
glycidyl or a group -CH2-CH(OH)-Z or CONH-Z, where Z is hydrogen, methyl or phenyl; or
When n = 2,
G2 is C2-C12alkylene, C6-C12arylene, xylylene or -CH2CH(OH)-CH2- or -CH2-CH(OH)-CH2-O-D-O- group, where D is C2-C10alkylene, C6-C15arylene, C6-C12cycloalkylene;
or, when n = 1, G1 and G2 may together be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2-dicarboxylic acid or 1,3-dicarboxylic acid.
[0049] A C2-C18alkanoyl group G1 may be, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, preferably acetyl.
[0051] A C2-C8alkenyl group G2 may be, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
[0052] A hydroxy-, cyano-, alkoxycarbonyl- or carbamido-substituted C1-C4alkyl group G2 may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
[0053] A C2-C12alkylene group G2 may be, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
[0054] A C6-C15arylene group G2 may be, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-biphenylene.
[0056] For instance, the present hydroxylamine esters are of the formula IC
Where
n is 1 or 2 and Ra, R1', R2' and R3' are as defined under the formula IA; and
G3 is C2-C8alkylene, C2-C8hydroxyalkylene or C4-C24acyloxyalkylene when n = 1 or is the group (-CH2)2C(CH2-)2 when n = 2.
[0057] For example, the present hydroxylamine esters are of the formula IC, where
Ra, R1', R2' and R3' are as defined under the formula IA and
G3 is C2-C8alkylene or C4-C24acyloxyalkylene.
[0058] A C2-C8alkylene or C2-C8hydroxyalkylene group G3 may be, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
[0060] The hydroxylamine esters may be of the formulae ID, IE or IF
Where
n is 1 or 2 and Ra, R1', R2 and R3' are as defined under the formula IA; and
G4 is hydrogen, C1-C12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl; and
G5 has the following meanings:
Whenn=1,
G5 is hydrogen, C1-C12alkyl, C3-C5alkenyl, C1-C9aralkyl, C5-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C10aryl, glycidyl or a group: -(CH2)p-COO-Q or -(CH2)p-O-CO-Q, where p is 1 or 2 and Q is C1-C4alkyl or phenyl; or
When n = 2,
G5 is C2-C12alkylene, C4-C12alkenylene, C6-C12arylene, the group -CH2-CH(OHFCH2-O-D-O-CH2-CH(OH)-CH2-, where D is C2-C10-alkylene, C6-C15arylene or C6-C12-cycloalkylene, or the group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2-, where Z' is hydrogen, C1-C18alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl;
T1 and T2 are each, independently of one another, hydrogen, C1-C18alkyl, C6-C10aryl or C1-C9aralkyl, each of which may be substituted by halogen or C1-C4-alkyl, or
T1 and T2 together with the carbon atom connecting them form a C5-C14cycloalkane ring.
[0061] The substituents C1-C12alkyl are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
[0062] Substituents defined as C1-C18-alkyl may be, for example, the above-mentioned groups or, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[0063] C2-C6Alkoxyalkyl is, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, 2-ethoxyethyl, 2- or 3-ethoxy-n-propyl, 2-n-butoxyethyl, 2-tert-butoxyethyl, 2-isopropoxyethyl or 2- or 3-n-propoxy-n-propyl.
[0064] A C3-C5alkenyl group G5 may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
[0065] C7-C9Aralkyl groups G5, T1 and T2 are preferably 2-phenethyl or benzyl. When T1 and T2 together with the carbon atom form a cycloalkane ring, this ring may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
[0066] A C2-C4hydroxyalkyl group G5 may be, for example, 2-hydroxyethyl, 2- or 3-hydroxy-n-propyl or 2-, 3- or 4-hydroxy-n-butyl.
[0067] A C6-C10aryl group G5, T1 and T2 is preferably phenyl or α- or β-naphthyl, each of which may be substituted by halogen or C1-C4alkyl.
[0068] A C2-C12alkylene group G5 may be, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
[0070] A C6-C12arylene group G5 may be, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-biphenylene.
[0071] A C2-C12alkanoyl group Z' is, for example, preferably acetyl and may also be propionyl, butyryl, n-octanoyl or n-dodecanoyl.
[0072] C2-C10Alkylene, C6-C15arylene and C6-C12cycloalkylene groups D are as defined under formula IB.
[0073] The present hindered hydroxylamine esters may be of the formula IG
Where
n = 1 or 2 and G6 is a group:
[0074] Where Ra, R1', R2 and R3' are as defined under the formula IA, and R3' and R4' are each hydrogen or methyl or together form the substituent =O;
E is -O- or -NG1-,
A is C2-C6-alkylene or -(CH2)3-O-, and x is either 0 or 1;
G1 is hydrogen, C1-C12alkyl, C2-C5hydroxyalkyl or C5-C7cycloalkyl;
G7 is identical to G6 or is one of the groups -NG9G10, -OG11, -NHCH2OG11 or -N(CH2OG11)2;
When n=1, G8 is identical to G6 or G7; and,
When n=2, G8 is the group -E-B-E-, where B is C2-C8-alkylene or C2-C8-alkylene interrupted by 1 or 2 -NG9- groups, and G9 is C1-C12alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl or the groups:
G10 is C1-C12-alkyl, cyclohexyl, benzyl or C1-C4-hydroxyalkyl, and G11 is hydrogen, C1-C12-alkyl or phenyl; and
G9 and G10 are together C4-C5-alkylene or C4-C5oxaalkylene.
G9 and G10 may further be together, for example, C4-C5-alkylene, C4-C5oxaalkylene, e.g. tetramethylene, pentamethylene or 3-oxapentamethylene, or the corresponding
C4-C5thiaalkylene, e.g. the group
[0075] C1-C12Alkyl is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
[0076] C1-C4Hydroxyalkyl is, for example, 2-hydroxyethyl, 2- or 3-hydroxypropyl or 2-, 3- or 4-hydroxy-n-butyl.A C2-C6alkylene group A, may be, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
[0077] The hindered hydroxylamine ester compounds may be of the formula IH
Where n is an integer greater than two and R1', R2' and R3' are as defined under the formula IA; and B is a bivalent substituent.
[0078] B is, for example, C1-C12alkylene, e.g. methylene, ethylene, propylene, 2,2-dimethylpropylene or tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene, C6-C15arylene, e.g. a group:
Where X is a bivalent substituent, e.g. C1-C12alkylene as defined above, -O-, -(C=O)-, -S- or -S(=O)2-.
[0079] The present polyesters of formula (IH) may also correspond to compounds where the group
is partially replaced by suitable diols, which are derived, for example, from aliphatic, cycloaliphatic or aromatic diols.
[0080] The aliphatic diols may contain from 2 to 12 C-atoms, the cycloaliphatic diols may contain from 5 to 8 C-atoms and the aromatic diols may contain from 6 to 15 C-atoms.
[0081] Polyoxyalkylene glycols having molecular weights in the range from 150 to 40 000 are also possible.
[0082] Aromatic diols are compounds in which two hydroxy groups are bound to an aromatic hydrocarbon radical or to different aromatic hydrocarbon radicals.
[0083] The polyesters may be branched by means of small amounts, e.g. from 0.1 to 3.0 mol%, based on the dicarboxylic acids present, of more than bifunctional monomers (e.g. pentaerythritol, trimellitic acid, 1,3,5-tri(hydroxyphenyl)benzene, 2,4-dihydroxybenzoic acid or 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane).
[0084] Suitable aliphatic diols are linear and branched aliphatic glycols, in particular those having from 2 to 12, preferably from 2 to 6, C-atoms in the molecule, e.g. ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, pentyl glycol, neopentyl glycol, 1,6-hexanediol, 1,12-dodecanediol.
[0085] A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane. Further suitable diols are, for example, 1,4-bis(hydroxymethyl)cyclohexane, aromatic-aliphatic diols such as p-xylylene glycol or 2,5-dichloro-p-xylylene glycol, 2,2-(β-hydroxyethoxyphenyl)propane and also polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylenediols are preferably linear and contain, in particular, from 2 to 4 C-atoms.
[0086] Preferred diols are alkylene diols, 1,4-dihydroxycyclohexane and 1,4-bis(hydroxymethyl)cyclohexane. Particular preference is given to ethylene glycol, 1,4-butanediol and 1,2- and 1,3-propylene glycol.
[0087] Further suitable aliphatic diols are the β-hydroxyalkylated, in particular β-hydroxyethylated, bisphenols such as 2,2-bis[4'-(β-hydroxyethoxy)phenyl]propane.
[0088] A further group of suitable aliphatic diols consists of the heterocyclic diols described in U.S. Pat. Spec. Nos. 3,867,400 and 3,954,790. Examples are: N,N'-bis(β-hydroxyethyl)-5,5-dimethylhydantoin, N,N'-bis(β-hydroxypropyl)-5,5-dimethylhydantoin, methylenebis[N-(β-hydroxyethyl)-5-methyl-5-ethylhydantoin], methylenebis[N-(β-hydroxyethyl)-5,5-dimethylhydantoin], N,N'-bis(β-hydroxyethyl)benzimidazolone, N,N'-bis(β-hydroxyethyl)(tetrachloro)benzimidazolone or N,N'-bis(β-hydroxyethyl)(tetrabromo)benzimidazolone.
[0089] Suitable aromatic diols are diphenols having one aromatic unit, in particular diols having two aromatic units which bear a hydroxy group on each aromatic unit. Aromatic units are to be understood as meaning aromatic hydrocarbon radicals such as phenylene or naphthylene. Apart from, for example, hydroquinone, resorcinol or 1,5-, 2,6- and 2,7-dihydroxynaphthalene, particular mention may be made of the bisphenols bis(p-hydroxyphenyl) ether or thioether, bis(p-hydroxyphenyl) sulphone, bis(p-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)biphenyl, phenylhydroquinone, 1,2-bis(p-hydroxyphenyl)ethane, 1-phenylbis(p-hydroxyphenyl)methane, diphenylbis(p-hydroxyphenyl)methane, diphenylbis(p-hydroxyphenyl)ethane, bis(3,5-dimethyl-4-hydroxyphenyl) sulphone, bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, bis(3,5-dimethyl-4-hydroxyphenyl)-m-diisopropylbenzene, 2,2-bis(3',5'-dimethyl-4'-hydroxyphenyl)propane, 1,1- or 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)hexafluoropropane, 1,1-dichloro- or 1,1,1-trichloro-2,2-bis(p-hydroxyphenyl)ethane, 1,1-bis(p-hydroxyphenyl)cyclopentane and in particular 2,2-bis(p-hydroxyphenyl)propane (bisphenol A) and 1,1-bis(p-hydroxyphenyl)cyclohexane (bisphenol C).
[0090] Examples of substituted or unsubstituted alkylene are methylene, ethylene, phenylmethylene, diphenylmethylene and methylphenylmethylene.
[0091] Examples of cycloalkylidene are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.
[0092] C6-C10Aryl is, for example, phenyl or naphthyl, but also comprised are C1-C4alkyl substituted phenyl. Examples for alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene.
[0093] Alkyl is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.
[0094] The addition of the hydroxylamine esters to the thermoplastic polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
[0095] The process is preferably carried out in an extruder by introducing the additive during processing.
[0096] Particularly preferred processing machines are single-screw extruders, contra-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co-kneaders. Processing machines may be used provided with at least one gas removal compartment to which a vacuum can be applied.
[0097] Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
[0098] For example, the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
[0099] The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
[0101] The polymers need to be subjected to an elevated temperature for a sufficient period of time during incorporation of additives. The temperature is generally above the softening point of the polymers.
[0102] In a preferred embodiment of the process of the present invention, a temperature range lower than 280°C, particularly from about 160°C to 280°C is employed. In a particularly preferred process variant, the temperature range from about 200°C to 270°C is employed.
[0103] The above-described hydroxylamine esters are suitable for reducing the molecular weight of polypropylene, propylene copolymers and polypropylene blends during compounding, where they effect degradation of the polymer chains. Provided are, for example, very uniform polypropylene polymers with a narrow molecular weight distribution. Such polypropylene is excellent for electret applications.
[0104] Incorporation can, alternatively, also be carried out at temperatures which do not yet cause decomposition of the polymers (latent compound). The polymers prepared in this way can subsequently be heated a second time and subjected to an elevated temperature for a sufficient period of time so that the desired polymer degradation occurs.
[0105] In the processes and compositions of the present invention the above-described hydroxylamine ester containing compounds are present in concentrations, based on the amount of the polymer, of from about 0.001 to 5.0% by weight, in particular from 0.01 to 2.0% by weight and particularly preferably from 0.02 to 1.0% by weight. The hydroxylamine esters can be added as individual compounds or as mixtures to the polymer.
[0106] Incorporation of additives into the polymers can be carried out, for example, by mixing the above-described hydroxylamine esters or mixtures thereof and, if desired, further additives into the polymers using the methods customary in process technology.
[0107] The hydroxylamine esters can also be added to the polymers in the form of a master batch in which these compounds are present, for example, in a concentration of from about 1.0 to 25.0% by weight. The present invention therefore further provides a concentrate in which the compounds of the invention are present in a concentration of about 1.0 - 25.0% by weight and which can be added to the thermoplastic polymer.
[0108] Another aspect of this invention is the co-use of certain other additives along with the present hydroxylamine esters. These certain other additives are incorporated in the same manner as the hydroxylamine esters.
[0109] For instance, the class of stabilizers of the hindered amine light stabilizers (HALS) other than the present hydroxylamine ester compounds are advantageously also employed in the present processes and compositions.
[0110] The present sterically hindered amine stabilizers contain at least one moiety of formula
Wherein the dotted lines represent bonds to groups and substituents;
Where G1, G2, G3, G4 and G5 are independently alkyl of 1 to 8 carbon atoms or G1 and G2 or G3 and G4 together are pentamethylene.
[0111] The hindered amines are disclosed, for example, in U.S. Pat. Spec. Nos. 5,004,770, 5,204,473, 5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145, 893, 5,216,156, 5,844,026, 5,980,783, 6,046,304, 6,117,995, 6,271,377, 6,297,299, 6,392,041, 6,376,584 and 6,472,456, and U.S. App. Nos. 09/714,717, filed Nov. 16,2000 and 10/485,377, filed August 6, 2002.
[0112] U.S. Pat. Spec. Nos. 6,271,377, 6,392,041 and 6,376,584, cited above, disclose hindered hydroxyalkoxyamine stabilizers.
[0113] Suitable hindered amines are selected from the group consisting of:
- 1) 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine
- 2) bis(2,2,6,6-Tetramethylpiperidin-4-yl)sebacate
- 3) bis(1-Acetoxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
- 4) bis(1,2,2,6,6-Pentamethyl-4-yl)sebacate
- 5) bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
- 6) bis(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
- 7) bis(1-Acyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
- 8) bis(1,2,2,6,6-Pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate
- 9) 2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine
- 10) bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate
- 11) 2,4-bis[(1-Cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine
- 12) 1-(2-Hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine
- 13) 1-(2-Hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine
- 14) 1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine
- 15) bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
- 16) bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate
- 17) 2,4-bis{N-[1-(2-Hydroxy-2-methy)propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine
- 18) 4-Benzoyl-2,2,6,6-tetramethylpiperidine
- 19) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate
- 20) 4-Stearyloxy-2,2,6,6-tetramethylpiperidine
- 21) bis(1-Octyloxy-2,2,6,6-tetramethylpiperidyl)succinate
- 22) 1,2,2,6,6-Pentamethyl-4-aminopiperidine
- 23) 2-Undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane
- 24) tris(2,2,6,6-Tetramethyl-4-piperidyl)nitrilotriacetate
- 25) tris(2-Hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidin-4-yl)propyl)nitrilotriacetate
- 26) tetrakis(2,2,6,6-Tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate
- 27) tetrakis(1,2,2,6,6-Pentamethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate
- 28) 1,1'-(1,2-Ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone)
- 29) 3-n-Octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione
- 30) 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione
- 31) 3-Dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidin-2,5-dione
- 32) 3-Dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione
- 33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine
- 34) The reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)-butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine)
- 35) The condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid
- 36) Linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine
- 37) Linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine
- 38) Linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine
- 39) Linear or cyclic condensates of N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine
- 40) The condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane
- 41) The condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane
- 42) The reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane and epichlorohydrine
- 43) Poly[methyl-(3-oxy-(2,2,6,6-tetramethylpiperidin-4-yl)propyl)] siloxane, CAS No. 182635-99-0
- 44) The reaction product of maleic acid anhydride-C18-C22-α-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine
- 45) The oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine
- 46) The oligomeric compound which is the condensation product of 4,4'-hexa-methylenebis(amino-1,2,2,6,6-pentaamethylpiperidine) and 2,4-dichloro-6-[(1,2,2,6,6-pentaamethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine
- 47) The oligomeric compound which is the condensation product of 4,4'-hexa-methylenebis(amino-1-propoxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine
- 48) The oligomeric compound which is the condensation product of 4,4'-hexa-methylenebis(amino-1-acyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-acyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine and
- 49) The product obtained by reacting a product, obtained by reacting 1,2-bis(3-aminopropylamino)ethane with cyanuric chloride, with 2,2,6,6-tetramethylpiperidin-4-yl-butylamine.
[0114] Also included are the sterically hindered N-H, N-methyl, N-methoxy, N-propoxy, N-octyloxy, N-cyclohexyloxy and N-(2-hydroxy-2-methylpropoxy) analogues of any of the above mentioned compounds.
[0115] The class of additives known as the hydroxyphenylalkylphosphonic esters or monoesters are also advantageously employed in the processes and compositions of this invention. The hydroxyphenylalkylphosphonic esters or monoesters are disclosed, for example, in U.S. Published App. No. 2004/0106767. The hydroxyphenylalkylphosphonic esters or monoesters are of the formula
Wherein
R6 is isopropyl, tert-butyl, cyclohexyl or cyclohexyl which is substituted by 1-3 C1-C4alkyl groups,
R7 is hydrogen, C1-C4alkyl, cyclohexyl or cyclohexyl which is substituted by 1-3 C1-C4alkyl groups,
R8 is C1-C20alkyl, unsubstituted or C1-C4alkyl-substituted phenyl or naphthyl,
R9 is hydrogen, C1-C20alkyl, unsubstituted or C1-C4alkyl-substituted phenyl or naphthyl; or corresponds to:
wherein
Mr+ is an r-valent metal cation,
p is 1, 2, 3, 4, 5 or 6, and
r is 1,2 or 3.
[0116] For example, the present hydroxyphenylalkylphosphonic ester or monoester is a compound of the formula P1 or P2:
[0117] The processes and compositions of the present invention may further include additives from the class of the aromatic tris-amide nucleating agents. The tris-amide nucleating agents are disclosed, for example, in Published U.S. App. Nos. 2005/0203226 and 10/544,508, filed February 9, 2004, and in WO 2004/072168.
[0118] The aromatic tris-amides are for instance of the formula
Wherein
R1, R2 and R3, independently of one another, are
C1-C20Alkyl, C2-C20alkyl substituted by C1-C10alkylamino, di(C1-C10alkyl)amino, C1-C10alkyloxy or hydroxy, C3-C20alkenyl, C5-C12cycloalkyl,C5-C12cycloalkyl substituted by 1-3 C1-C10alkyl, cyclohexylmethyl, cyclohexylmethyl substituted by 1, 2 or 3 C1-C10alkyl, C5-C9cycloalkenyl, C5-C9cycloalkenyl substituted by 1-3 C1-C10alkyl, phenyl, phenyl substituted by 1-3 substituents selected from the group consisting of C1-C10alkyl, C1-C10alkyloxy, hydroxy, halogen, trihalogenmethyl, trihalogenmethoxy, benzoyl, phenylamino, acylamino and phenylazo, C1-C9phenylalkyl, C1-C9phenylalkyl which is substituted on the phenyl by 1-3 substituents selected from the group consisting of C1-C10alkyl, C1-C10alkoxy and hydroxy,
naphthyl, naphthyl substituted by C1-C10alkyl, adamantyl, or a 5 to 6 membered heterocyclic group.
[0119] The aromatic tris-amides are, for example, of the formulae
Wherein .
R1, R2 and R3, or Y1, Y2 and Y3, or Z1, Z2 and Z3 independently of one another are C1-C20alkyl unsubstituted or substituted by 1-3 hydroxy;
C2-C20Alkenyl unsubstituted or substituted by 1-3 hydroxy;
C2-C20Alkyl interrupted by oxygen or sulphur;
C3-C12Cycloalkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
(C3-C12Cycloalkyl)-C1-C10alkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
bis[C3-C12Cycloalkyl]-C1-C10alkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
A bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by 1-3 C1-C20alkyl;
Phenyl unsubstituted or substituted by 1-3 substituents selected from the group consisting of C1-C20alkyl, C1-C20alkoxy, C1-C20alkylamino, di(C1-C20alkyl)amino, hydroxy and nitro;
Phenyl-C1-C20alkyl unsubstituted or substituted by 1-3 substituents selected from the group consisting of C1-C20alkyl, C3-C12cycloalkyl, phenyl, C1-C20alkoxy and hydroxy;
Phenylethenyl unsubstituted or substituted by 1-3 C1-C20alkyl;
Biphenyl-(C1-C10alkyl) unsubstituted or substituted by 1-3 C1-C20alkyl;
Naphthyl unsubstituted or substituted by 1-3 C1-C20alkyl;
Naphthyl-C1-C20alkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
Naphthoxymethyl unsubstituted or substituted by 1-3 C1-C20alkyl;
Biphenylenyl, fluorenyl, anthryl;
A 5- to 6-membered heterocyclic radical unsubstituted or substituted by 1-3 C1-C20alkyl;
A C1-C20hydrocarbon radical containing at least one halogen; or
Tri(C1-C10alkyl)silyl(C1-C10alkyl);
with the proviso that at least one of the radicals R1, R2 and R3, or Y1, Y2 and Y3, or Z1, Z2 and Z3 is
Branched C3-C20alkyl unsubstituted or substituted by at least one hydroxy;
C2-C20Alkyl interrupted by oxygen or sulphur;
C3-C12Cycloalkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
(C3-C12Cycloalkyl)-C1-C10alkyl unsubstituted or substituted by 1-3 C1-C20alkyl;
A bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by 1-3 C1-C20alkyl;
Phenyl unsubstituted or substituted by 1-3 substituents selected from the group consisting C1-C20alkyl, C1-C20alkoxy, C1-C20alkylamino, di(C1-C20alkyl)amino, hydroxy and nitro;
Phenyl-C1-C20alkyl unsubstituted or substituted by 1-3 substituents selected from the group consisting of C1-C20alkyl, C3-C12cycloalkyl, phenyl, C1-C20alkoxy and hydroxy;
Biphenyl-(C1-C10alkyl)unsubstituted or substituted by 1-3 C1-C20alkyl;
Naphthyl-C1-C20alkyl unsubstituted or substituted by 1-3 C1-C20alkyl; or
Tri(C1-C10alkyl)silyl(C1-C10alkyl).
[0120] According to a preferred embodiment,
At least one of the radicals R1, R2 and R3, or Y1, Y2 and Y3, or Z1, Z2 and Z3 is Branched C3-C20alkyl, or
C3-C12Cycloalkyl unsubstituted or substituted by 1-3 C1-C20alkyl.
[0121] According to a particular preferred embodiment, at least one of the radicals R1' R2 and R3, or Y1, Y2 and Y3, or Z1, Z2 and Z3 is
branched C3-C10alkyl.
[0122] The further additives of the hindered amine light stabilizers, the hydroxyphenylalkylphosphonic esters or monoesters and the aromatic tris-amide nucleating agents are employed at the same levels as the present hydroxylamine esters.
[0123] The following Examples further illustrate the present invention. All percentages are in weight percent unless otherwise indicated.
Example 1
[0124] The following hindered hydroxylamine ester compounds are prepared according to published U.S. App. No. 2003/0216494.
[0126] The above hydroxylamine ester compounds are individually melt compounded in polypropylene at a level of 0.05 weight percent. 0.1 parts by weight of calcium stearate is also incorporated into the polypropylene. The resultant granules are spun by means of a melt-blown method to obtain non-woven fabrics. The fabrics are subjected to a corona treatment.
[0127] The non-woven fabrics exhibit excellent thermal stability. The fabrics also hold the electric charge for a long period of time, that is the fabrics have good charge stability.
Example 2
[0128] Polypropylene with melt flow index (MFI) of 35, 25, or 12 are tumble mixed to contain 5.0% by weight of a sterically hindered amine (HALS), 2.0% by weight of a sterically hindered hydroxyphenylalkylphosphonic monoester (HPPME), or 0.5% by weight of an aromatic tri-samide (TA), based on the weight of polymer.
[0129] These mixes are individually compounded using a Leistritz 27 mm twin screw extruder. The melt is cooled in water a trough and the strand is converted into pellets via a Conair - Jetro Model 304 pelletizer. The pellets collected are considered the master batches. Polypropylene is tumble mixed with the appropriate amounts of master batch and a present hindered hydroxylamine ester (HHAE) for each of the evaluations. The tumble mixing is via Marion Mixer SPS 1224 which is a paddle type slow RPM mixer. These are considered the final mixes. Final mixes at 45 kg each are converted into melt blown non-woven textiles using a 500 mm Reifenhäuser Melt Blowing Pilot Line. The polypropylene webs are then treated by corona discharge.
[0130] The samples are tested using TSI Filter Tester (Model 8130) in which sodium chloride aerosol is sprayed at 32 I per minute using a test area of 100 cm2. Results are found in the following Tables.
| Formulation | Basis Weight (g/m2) |
Filtration Efficiency (%) | Filtration Efficiency Loss (%) |
||
| Before charging |
After charging |
Charged & aged (70°C/24 hrs) |
|||
| Polypropylene (PP) / 3% HHAE | 30.8 | 27.4 | 91.4 | 84.9 | 7.2 |
| PP / 3% HHAE/ 0.5% HALS | 30.9 | 39.9 | 93.6 | 86.0 | 8.2 |
| PP / 3% HHAE/ 0.5% HPPME | 30.7 | 22.0 | 88.6 | 85.9 | 3.1 |
| PP / 3% HHAE/ 0.05% TA | 30.7 | 27.0 | 90.9 | 89.5 | 1.6 |
| Formulation | Basis Weight (g/m2) |
Filtration Efficiency (%) | Filtration Efficiency Loss (%) |
||
| Before charging |
After charging |
Charged & aged (70°C/24 hrs) |
|||
| Polypropylene (PP)/3% HHAE | 30.6 | 21.6 | 90.5 | 78.5 | 13.7 |
| PP/3% HHAE / 0.5% HALS | 30.9 | 38.7 | 96.7 | 89.7 | 7.3 |
| PP / 3% HHAE / 0.5% HPPME | 30.8 | 40.9 | 97.5 | 96.5 | 1.0 |
| PP/3% HHAE / 0.05% TA | 30.6 | 41.6 | 97.2 | 96.7 | 0.5 |
| Formulation | Basis Weight (g/m2) |
Filtration Efficiency (%) | Filtration Efficiency Loss (%) |
||
| Before charging |
After charging |
Charged & aged (70°C/24 hrs) |
|||
| Polypropylene (PP)/ 2.5% HHAE | 30.8 | 41.3 | 85.9 | 74.3 | 13.5 |
| PP/ 2.5% HHAE/ 0.5% HALS | 29.6 | 21.7 | 80.4 | 59.4 | 26.1 |
| PP/ 2.5% HHAE/ 0.5% HPPME | 30.2 | 26.0 | 86.6 | 84.1 | 2.9 |
| PP/ 2.5% HHAE/ 0.05% TA | 30.1 | 29.7 | 86.8 | 84.8 | 2.3 |
Where
Ra' is a monoacyl or diacyl radical;
R1 - R4 are each C1-C6alkyl; and
R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl; or
R5 and R6 are together oxygen; and
subjecting the blend to an electret treatment.
Where
n is an integer from 1 to 4,
Ra is acyl and R1', R2' and R3' are each, independently of one another, hydrogen or methyl; and
G has the following meanings:
When n=1,
G is hydrogen, C1-C18alkyl which may be interrupted by at least one oxygen atom, 2-cyanoethyl, benzyl,
glycidyl, the monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated
or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent
silyl radical, preferably the acyl radical of an aliphatic carboxylic acid having
from 2 to 18 C-atoms, of a cycloaliphatic carboxylic acid having from 7 to 15 C-atoms,
of an α,β-unsaturated carboxylic acid having from 3 to 5 C-atoms or of an aromatic
carboxylic acid having from 7 to 15 C-atoms, where the carboxylic acid may be substituted
in the aliphatic, cycloaliphatic or aromatic part by from 1 to 3 -COOZ1 groups, where Z1 is hydrogen, C1-C20alkyl, C3-C12alkenyl, C5-C7cycloalkyl, phenyl or benzyl; or
When n = 2,
G is C2-C12alkylene, C4-C12alkenylene, xylylene, the divalent acid radical of an aliphatic, cycloaliphatic, araliphatic
or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid, or a
divalent silyl radical, preferably the acyl radical of an aliphatic dicarboxylic acid
having from 2 to 36 C-atoms, of a cycloaliphatic or aromatic dicarboxylic acid having
from 8 to 14 C-atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid
having from 8 to 14 C-atoms, where the dicarboxylic acid may be substituted in the
aliphatic, cycloaliphatic or aromatic part by 1 or 2 -COOZ1 groups, where Z1 is as defined above; or
When n = 3,
G is the trivalent acid radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic
acid, where the radical may be substituted in the aliphatic, cycloaliphatic or aromatic
part by -COOZ1, where Z1 is as defined above, or the trivalent acid radical of an aromatic tricarbamic acid
or a phosphorus-containing acid, or a trivalent silyl radical; and
When n = 4,
G is the tetravalent acid radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic
acid.
Where
n is 1 or 2 and Ra is acyl and R1', R2' and R3' are independently hydrogen or methyl; and
G3 is C2-C8alkylene, C2-C8hydroxyalkylene or C4-C24acyloxyalkylene when n = 1 or is the group (-CH2)2C(CH2-)2 when n = 2.
Where
Ra is acyl and R1', R2' and R3' are independently hydrogen or methyl and
G3 is C2-C8alkylene or C4-C24acyloxyalkylene.
Where
n = 1 or 2 and G6 is a group:
E is -O- or -NG1-;
A is C2-C6-alkylene or -(CH2)3-O-, and x is either 0 or 1;
G1 is hydrogen, C1-C12alkyl, C2-C5hydroxyalkyl or C5-C7cycloalkyl;
G7 is identical to G6 or is one of the groups -NG9G10, -OG11, -NHCH2OG11 or -N(CH2OG11)2;
When n=1, G8 is identical to G6 or G7; and,
When n=2, G8 is the group -E-B-E-, where B is C2-C8-alkylene or C2-C8-alkylene interrupted by 1 or 2 -NG9- groups, and G9 is C1-C12alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl or the groups:
G10 is C1-C12-alkyl, cyclohexyl, benzyl or C1-C4-hydroxyalkyl, and G11 is hydrogen, C1-C12-alkyl or phenyl; and
G9 and G10 are together C4-C5-alkylene or C4-C5oxaalkylene.
wobei
Ra' ein Monoacyl- oder Diacylrest ist;
R1 - R4 jeweils C1-C6-Alkyl sind; und
R5 und R6 jeweils unabhängig voneinander Wasserstoff, C1-C6-Alkyl oder C6-C10-Aryl sind;
oder
R5 und R6 zusammen Sauerstoff sind; und
das Unterziehen der Mischung einer Elektretbehandlung umfasst.
wobei
n eine ganze Zahl von 1 bis 4 ist,
Ra Acyl ist und R1', R2' und R3' jeweils unabhängig voneinander Wasserstoff oder Methyl sind; und
G die folgenden Bedeutungen hat:
Wenn n=1,
ist G Wasserstoff, C1-C18-Alkyl, das von mindestens einem Sauerstoffatom unterbrochen sein kann, 2-Cyanoethyl,
Benzyl, Glycidyl, der einwertige Rest einer aliphatischen, cycloaliphatischen, araliphatischen,
ungesättigten oder aromatischen Carbonsäure, Carbaminsäure oder phosphorhaltigen Säure
oder ein einwertiger Silylrest, bevorzugt der Acylrest einer aliphatischen Carbonsäure
mit 2 bis 18 C-Atomen, einer cycloaliphatischen Carbonsäure mit 7 bis 15 C-Atomen,
einer α,β-ungesättigten Carbonsäure mit 3 bis 5 C-Atomen oder einer aromatischen Carbonsäure
mit 7 bis 15 C-Atomen, wobei die Carbonsäure in dem aliphatischen, cycloaliphatischen
oder aromatischen Teil durch 1 bis 3 -COOZ1 Gruppen substituiert sein kann, wobei Z1 Wasserstoff, C1-C20-Alkyl, C3-C12-Alkenyl, C5-C7-Cycloalkyl, Phenyl oder Benzyl ist; oder
wenn n=2,
ist G C2-C12-Alkylen, C4-C12-Alkenylen, Xylylen, der zweiwertige Rest einer aliphatischen, cycloaliphatischen,
araliphatischen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder phosphorhaltigen
Säure oder ein zweiwertiger Silylrest, bevorzugt der Acylrest einer aliphatischen
Dicarbonsäure mit 2 bis 36 C-Atomen, einer cycloaliphatischen oder aromatischen Dicarbonsäure
mit 8 bis 14 C-Atomen oder einer aliphatischen, cycloaliphatischen oder aromatischen
Dicarbaminsäure mit 8 bis 14 C-Atomen, wobei die Dicarbonsäure in dem aliphatischen,
cycloaliphatischen oder aromatischen Teil durch 1 oder 2 -COOZ1 Gruppen substituiert sein kann, wobei Z1 wie oben definiert ist; oder wenn n=3,
ist G der dreiwertige Säurerest einer aliphatischen, cycloaliphatischen oder aromatischen
Tricarbonsäure, wobei der Rest in dem aliphatischen, cycloaliphatischen oder aromatischen
Teil durch -COOZ1 substituiert sein kann, wobei Z1 wie oben definiert ist, oder der dreiwertige Säurerest einer aromatischen Tricarbaminsäure
oder einer phosphorhaltigen Säure oder ein dreiwertiger Silylrest; und
wenn n=4,
ist G der vierwertige Säurerest einer aliphatischen, cycloaliphatischen oder aromatischen
Tetracarbonsäure.
wobei
n 1 oder 2 ist und Ra Acyl ist und R1', R2' und R3' unabhängig Wasserstoff oder Methyl sind;
und
G3 C2-C8-Alkylen, C2-C8-Hydroxyalkylen oder C4-C24-Acyloxyalkylen ist, wenn n=1 ist oder die Gruppe (-CH2)2C(CH2-)2 ist, wenn n=2 ist.
wobei
Ra Acyl ist und R1', R2' und R3' unabhängig Wasserstoff oder Methyl sind und
G3 C2-C8-Alkylen oder C4-C24-Acyloxyalkylen ist.
wobei
n=1 oder 2 und G6 eine Gruppe ist:
E -O- oder -NG1- ist;
A C2-C6-Alkylen oder -(CH2)3-O- ist und x entweder 0 oder 1 ist;
G1 Wasserstoff, C1-C12-Alkyl, C2-C5-Hydroxyalkyl oder C5-C7-Cycloalkyl ist;
G7 identisch zu G6 ist oder eine der Gruppen -NG9G10, -OG11, -NHCH2OG11 oder -N(CH2OG11)2 ist;
wenn n=1, ist G8 identisch zu G6 oder G7; und,
wenn n=2, ist G8 die Gruppe -E-B-E-, wobei B C2-C8-Alkylen oder C2-C8-Alkylen, unterbrochen durch 1 oder 2 -NG9-Gruppen, ist und G9 C1-C12-Alkyl, Cyclohexyl, Benzyl oder C1-C4-Hydroxyalkyl darstellt oder die Gruppen ist:
G10 C1-C12-Alkyl, Cyclohexyl, Benzyl oder C1-C4-Hydroxyalkyl ist und G11 Wasserstoff, C1-C12-Alkyl oder Phenyl ist; und
G9 und G10 zusammen C4-C5-Alkylen oder C4-C5-Oxaalkylen sind.
dans laquelle
Ra' est un radical monoacyle ou diacyle ;
R1 à R4 sont respectivement un groupe alkyle en C1 à C6 ; et
R5 et R6 sont respectivement, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe
alkyle en C1 à C6 ou aryle en C6 à C10;
ou
R5 et R6 sont conjointement un atome d'oxygène ; et
la soumission du mélange à un traitement par électret.
dans laquelle
n est un nombre entier de 1 à 4,
Ra est un groupe acyle et R1', R2' et R3' sont chacun, indépendamment les uns des autres, un atome d'hydrogène ou un groupe méthyle ; et
G a les significations suivantes :
si n = 1,
G est un atome d'hydrogène, un groupe alkyle en C1 à C18 qui peut être interrompu par au moins un atome d'oxygène, un groupe 2-cyanoéthyle,
benzyle, glycicyle, le radical monovalent d'un acide carboxylique, acide carbamique
ou acide contenant du phosphore aliphatique, cycloaliphatique, araliphatique, insaturé
ou aromatique, ou un radical silyle monovalent, de préférence, le radical acyle d'un
acide carboxylique aliphatique ayant de 2 à 18 atomes de carbone ou un acide carboxylique
cycloaliphatique ayant 7 à 15 atomes de carbone d'un acide α, β-carboxylique insaturé
ayant 3 à 5 atomes de carbone ou d'un acide carboxylique aromatique ayant 7 à 15 atomes
de carbone, l'acide carboxylique pouvant être substitué dans la partie aliphatique,
cycloaliphatique ou aromatique par de 1 à 3 groupes -COOZ1, où Z1 est un atome d'hydrogène, un groupe alkyle en C1 à C20, alcényle en C3 à C12, cycloalkyle en C5 à C7, phényle ou benzyle ; ou
si n=2,
G est un groupe alkylène en C2 à C12, alcénylène en C4 à C12, xylylène, le radical acide divalent d'un acide dicarboxylique, acide dicarbamaique
ou acide contenant du phosphore, aliphatique, cycloaliphatique, araliphatique ou aromatique,
ou un radical silyle divalent, de préférence, le radical acyle d'un acide dicarboxylique
aliphatique ayant de 2 à 36 atomes de carbone, d'un acide dicarboxylique cycloaliphatique
ou aromatique ayant de 8 à 14 atomes de carbone ou d'un acide carbamique cycloaliphatique
ou aromatique ayant de 8 à 14 atomes de carbone, l'acide dicarboxylique pouvant être
substitué dans la partie aliphatique, cycloaliphatique ou aromatique par 1 ou 2 groupes
-COOZ1, où Z1 est tel que défini ci-dessus ; ou
si n = 3,
G est le radical acide trivalent d'un acide tricarboxylique aliphatique, cycloaliphatique
ou aromatique, le radical pouvant être substitué dans la partie aliphatique, cycloaliphatique
ou aromatique par -COOZ1, Z1 étant tel que défini ci-dessus, ou le radical acide trivalent d'un acide tricarbamique
aromatique ou un acide contenant du phosphore, ou un radical silyle trivalent ; et
si n = 4,
G est le radical acide tétravalent d'un acide tétracarboxylique aliphatique, cycloaliphatique
ou aromatique.
dans laquelle
n vaut 1 ou 2 et Ra est un groupe acyle et R1', R2' et R3' sont indépendamment un atome d'hydrogène ou un groupe méthyle ; et
G3 est un groupe alkylène en C2 à C8, hydroxyalkylène en C2 à C8 ou acyloxyalcylène en C4 à C24, lorsque n = 1 ou est le groupe (-CH2)2C(CH2-)2, lorsque n = 2.
dans laquelle
Ra est un groupe acyle et R1', R2' et R3' sont indépendamment, un atome d'hydrogène ou un groupe méthyle et
G3 est un groupe alkylène en C2 à C8 ou acyloxyalkylène en C4 à C24.
dans laquelle
n = 1 ou 2 est G6 est un groupe :
dans laquelle Ra est un groupe acyle et R1', R2' et R3' sont indépendamment, un atome d'hydrogène ou un groupe méthyle, et R3' et R4' sont chacun un atome d'hydrogène ou un groupe méthyle, ou forment conjointement le substituant =O ; E est - O- ou -NG1- ;
A est un groupe alkylène en C2 à C6 ou -(CH2)3-O et x vaut 0 ou 1 ;
G1 est un atome d'hydrogène, un groupe alkyle en C1 à C12, hydroxyalkyle en C2 à C5 ou cycloalkyle en C5 à C7 ;
G7 est identique à G6 ou est l'un des groupes NG9G10, -OG11, -NHCH2OG11 ou -N(CH2OG11)2 ;
où n 1, G8 est identique à G6 ou G7; et
si n = 2, G8 est le groupe -E-B-E-, lorsque B est un groupe alkylène en C2 à C8 ou alkylène en C2 à C8 interrompu par 1 ou 2 groupes -NG9- et G8 est un groupe alkyle en C1 à C12, cyclohexyle, benzyle ou hydroxyalkyle en C1 à C4 ou les groupes :
G10 est un groupe alkyle en C1 à C12, cyclohexyle, benzyle ou hydroxyalkyle en C1 à C4 et G11 est un atome d'hydrogène, un groupe alkyle en C1 à C12 ou un groupe phényle ; et
G9 et G10 sont conjointement un groupe alkylène en C4 à C5 ou oxaalkylène en C4 à C5.
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This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
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